1. Field of the Invention
The present invention relates to conformance additives, to conformance treatment fluids made therefrom, to methods of improving conformance in a well. In another aspect, the present invention relates to conformance additives comprising polymer and fibers, to conformance treatment fluids made therefrom, to methods of improving conformance in a well using such fluids.
2. Description of the Related Art
In the production of hydrocarbons from subterranean hydrocarbon bearing formations, poor vertical conformance results from the vertical juxtaposition of relatively high permeability geologic zones to relatively low permeability zones within the subterranean formation. Poor areal conformance results from the presence of high permeability streaks and high permeability anomalies within the formation matrix, such as vertical fractures and networks of the same, which have very high permeability relative to the formation matrix. Fluids generally exhibit poor flow profiles and sweep efficiencies in subterranean formations having poor vertical or areal conformance. Poor conformance is particularly a problem where vertical heterogeneity and/or fracture networks or other structural anomalies are in fluid communication with a subterranean wellbore across which fluids are injected or produced.
The prior art is replete with a number of attempts to remedy conformance problems. For example, U.S. Pat. Nos. 3,762,476; 3,981,363; 4,018,286; and 4,039,029 to Gall or Gall et al describe various processes wherein gel compositions are formed in high permeability zones of subterranean formations to reduce the permeability therein. According to U.S. Pat. No. 3,762,476, a polymer such as polyacrylamide is injected into a formation followed sequentially by a crosslinking agent. The sequentially injected slugs are believed to permeate the treatment zone of the formation and gel in situ.
U.S. Pat. Nos. 4,683,949 and 4,744,419 both to Sydansk et al., both note that it is generally held that effective polymer/crosslinking agent systems necessitate sequential injection of the gel components because gel systems mixed on the surface often set up before they can effectively penetrate the treatment region. Both Sydansk et al. patents further note that in practice, treatments such as that disclosed in U.S. Pat. No. 3,762,476 using sequentially injected gel systems have proven unsatisfactory because of the inability to achieve complete mixing and gelation in the formation. As a result, gels only form at the interface of the unmixed gel components and often in regions remote from the desired treatment region.
Both of the Sydansk et al. patents purport to overcome a then-existing need in the art for a gelation process capable of forming gels having a predetermined gelation rate, strength, and stability to satisfy the particular demands of a desired treatment region in a subterranean hydrocarbon-bearing formation, through the use of a high molecular weight water-soluble acrylamide polymer, a chromium III/carboxylate complex cross-linking agent.
U.S. Pat. No. 5,377,760 to Merrill notes that while the polymer system of Sydansk et al. ""949 was an improvement over prior art systems which required sequential injection of the polymer components, difficulty was still encountered in employing the ""949 polymer system to plug large fissures because the larger masses of polymer required often lack the necessary strength to resist the pressures to which they are exposed. Merrill proposes the incorporation of fibers in the polymer by mixing the fibers with the polymer solution at the surface.
U.S. Pat. No. 3,701,384 discloses a method of sealing thief zones in a subterranean formation by plugging pores with a solid material. A slurry of finely divided inorganic solids is injected into the formation together with an aqueous colloidal dispersion of a water-insoluble metal hydroxide in a dilute aqueous solution of a high-molecular-weight organic polymeric polyelectrolyte. The preferred polymer solution contains between about 0.01 and about 0.2 percent by weight of high molecular weight polyacrylamide or hydrolyzed polyacrylamide. At these concentrations, the dissolved polymer causes the suspended solids to flocculate, thereby blocking pores in the formation. The tested inorganic solids which interacted with the polymer solution to form strong solids included finely ground asbestos fibers and magnesium oxide. However, asbestos is undesirable for use today, due to its carcinogenicity.
Another approach taken by the prior art is to pump a slurry containing a mixture of flexible fibers and a bonding agent into highly permeable portions of a formation interval. An agent which precipitates or gels the bonding agent is then injected into the interval. The goal of the method is to build up a filter cake of fibers on the permeable formation as a result of the fibers being deposited out of the slurry as the slurry flows through, the permeable formation, and then bond the fibers of the filter cake in place. Examples of such a method are disclosed in U.S. Pat. Nos. 3,593,798, 3,949,811 and 3,462,958.
Larger fissures are bridged according to the disclosure of U.S. Pat. No. 2,708,973 by setting fibrous plants in place in the fissure, after which cement is added, thereby building on the framework of the plants. While such a method can bridge larger gaps, the process is impractical for use in deep formations that extend over a large area.
U.S. Pat. No. 3,374,834 discloses a method of stabilizing earth formations by injecting an aqueous solution of gelling material which contains finely divided inert solids and needle-like crystals of silicate materials which act as a suspending agent to prevent premature settling out of the solids. The resulting gel does not, however, provide the desired combination of strength, economy, ease of mixing and ability to be readily introduced into a formation.
However, in spite of the advancements in the prior art, there still need for further innovation in the conformance improvement arts.
Specifically, Merrill""s teaching of mixing the fibers with the polymer solution requires a multiplicity of storage and mixing tanks, and a metering system which must be operated during the operation of the well. Specifically, a first tank will store a water and polymer solution, a second tank will store a water and cross-linking solution, and a third tank will be used to mix fibers with polymer solution from the first tank to create a polymer/fiber slurry. This polymer/fiber slurry is then metered from the third tank and combined with cross-linking solution metered from the second tank to the well bore.
Thus, there is a need for a conformance additive which would allow for simplification of the mixing equipment.
There is another need a conformation method allowing for a simplification of the mixing equipment.
These and other needs in the art will become apparent to those of skill in the art upon review of this specification, including its drawings and claims.
It is an object of the present invention to provide for further innovation in the conformance improvement arts.
It is another object of the present invention to provide for a conformance additive which will allow for the simplification of the mixing equipment.
It is even another object of the present invention to provide for a conformance method will allow for the simplification of the mixing equipment.
These and other objects of the present invention will become apparent to those of skill in the art upon review of this specification, including its drawings and claims.
According to one embodiment of the present invention there is provided a conformance additive comprising a dry mixture of water soluble crosslinkable polymer, a crosslinking agent, and a reinforcing material selected from among fibers and comminuted plant materials. In preferred embodiments, polymer is an a carboxylate-containing polymer and the crosslinking agent is a chromic carboxylate complex. In other preferred embodiments, the reinforcing material may comprise hydrophobic fibers selected from among nylon, rayon, and hydrocarbon fibers, and/or hydrophilic fibers selected from among glass, cellulose, carbon, silicon, graphite, calcined petroleum coke, and cotton fibers. The comminuted plant material is selected from the group of comminuted plant materials of nut and seed shells or hulls of almond, brazil, cocoa bean, coconut, cotton, flax, grass, linseed, maize, millet, oat, peach, peanut, rice, rye, soybean, sunflower, walnut, and wheat; rice tips; rice straw; rice bran; crude pectate pulp; peat moss fibers; flax; cotton; cotton linters; wool; sugar cane; paper; bagasse; bamboo; corn stalks; sawdust; wood; bark; straw; cork; dehydrated vegetable matter; whole ground corn cobs; corn cob light density pith core; corn cob ground woody ring portion; corn cob chaff portion; cotton seed stems; flax stems; wheat stems; sunflower seed stems; soybean stems; maize stems; rye grass stems; millet stems; and mixtures thereof.
According to another embodiment of the present invention, there is provided a method of forming a conformance fluid. The method generally includes taking the above conformance additive and contacting it with water or other aqueous solution.
According to even another embodiment of the present invention, there is provided a method of for plugging an opening in a subterranean formation. The method generally includes contacting the above described conformance additive with water or an aqueous solution to for a conformance fluid. The method then includes injecting the conformance fluid into the formation.
These and other embodiments of the present invention will become apparent to those of skill in the art upon review of this specification and claims.
The conformance additive of the present invention includes polymer, cross-linking agent and either fibers or comminuted particles of plant materials. In a preferred embodiment of the present invention, the conformance additive is a dry mixture of polymer, cross-linking agent and either fibers or comminuted particles of plant materials.
Any suitable relative amounts of the polymer, cross-linking agent and either fibers or comminuted particles of plant materials may be utilized in the present invention provided that the desired conformance results are achieved. Generally, the fibers or comminuted particles will comprise in the range of about 1 to about 99 weight percent, preferably in the range of about 25 to about 90 weight percent, more preferably in the range of about 50 to about 80 weight percent, and even more preferably in the range of about 70 to about 75 weight percent, all based on the total with of the polymer, fibers and particles. A suitable amount of crosslinking agent is provided to reach the desired amount of crosslinking. Suitable amounts of dispersants, retarders, accelerants, and other additives may be provided as necessary or desired.
The polymer utilized in the practice of the present invention is preferably water soluble and must be capable of being pumped as a liquid and subsequently crosslinked in place to form a substantially non-flowing crosslinked polymer which has sufficient strength to withstand the pressures exerted on it. Moreover, it must have a network structure capable of incorporating reinforcing fibers.
While any suitable water soluble polymer may be utilized, the preferred polymer utilized in the practice of the present invention is a carboxylate-containing polymer. This preferred carboxylate-containing polymer may be any crosslinkable, high molecular weight, water-soluble, synthetic polymer or biopolymer containing one or more carboxylate species.
For an example of polymers and crosslinking agents suitable for use herein and details regarding their making and use, please see U.S. Pat. Nos. 4,683,949 and 4,744,419, both incorporated herein by reference.
The average molecular weight of the carboxylate-containing polymer utilized in the practice of the present invention is in the range of about 10,000 to about 50,000,000, preferably in the range of about 100,000 to about 20,000,000, and most preferably in the range of about 200,000 to about 15,000,000.
Biopolymers useful in the present invention include polysaccharides and modified polysaccharides. Non-limiting examples of biopolymers are xanthan gum, guar gum, carboxymethylcellulose, o-carboxychitosans, hydroxyethylcellulose, hydroxypropylcellulose, and modified starches. Non-limiting examples of useful synthetic polymers include acrylamide polymers, such as polyacrylamide, partially hydrolyzed polyacrylamide and terpolymers containing acrylamide, acrylate, and a third species. As defined herein, polyacrylamide (PA) is an acrylamide polymer having substantially less than 1% of the acrylamide groups in the form of carboxylate groups. Partially hydrolyzed polyacrylamide (PHPA) is an acrylamide polymer having at least 1%, but not 100%, of the acrylamide groups in the form of carboxylate groups. The acrylamide polymer may be prepared according to any conventional method known in the art, but preferably has the specific properties of acrylamide polymer prepared according to the method disclosed by U.S. Pat. No. Re. 32,114 to Argabright et al incorporated herein by reference.
Any crosslinking agent suitable for use with the selected polymer may be utilized in the practice of the present invention. Preferably, the crosslinking agent utilized in the present invention is a chromic carboxylate complex.
The term xe2x80x9ccomplexxe2x80x9d is defined herein as an ion or molecule containing two or more interassociated ionic, radical or molecular species. A complex ion as a whole has a distinct electrical charge while a complex molecule is electrically neutral. The term xe2x80x9cchromic carboxylate complexxe2x80x9d encompasses a single complex, mixtures of complexes containing the same carboxylate species, and mixtures of complexes containing differing carboxylate species.
The chromic carboxylate complex useful in the practice of the present invention includes at least one or more electropositive chromium III species and one or more electronegative carboxylate species. The complex may advantageously also contain one or more electronegative hydroxide and/or oxygen species. It is believed that, when two or more chromium III species are present in the complex, the oxygen or hydroxide species may help to bridge the chromium III species. Each complex optionally contains additional species which are not essential to the polymer crosslinking function of the complex. For example, inorganic mono- and/or divalent ions, which function merely to balance the electrical charge of the complex, or one or more water molecules may be associated with each complex. Non-limiting representative formulae of such complexes include:
[Cr3(CH3CO2)6(OH)2]1+;
[Cr3(CH3CO2)6(OH)2]NO3xc2x76H2O;
[Cr3(CH3CO2)6(OH)2]3+; and
xe2x80x83[Cr3(CH3CO2)6(OH)2](CH3CO2)3xc2x7H2O.
xe2x80x9cTrivalent chromiumxe2x80x9d and xe2x80x9cchromic ionxe2x80x9d are equivalent terms encompassed by the term xe2x80x9cchromium IIIxe2x80x9d species as used herein.
The carboxylate species are advantageously derived from water-soluble salts of carboxylic acids, especially low molecular weight mono-basic acids. Carboxylate species derived from salts of formic, acetic, propionic, and lactic acid, substituted derivatives thereof and mixtures thereof are preferred. The preferred carboxylate species include the following water-soluble species: formate, acetate, propionate, lactate, substituted derivatives thereof, and mixtures thereof. Acetate is the most preferred carboxylate species. Examples of optional inorganic ions include sodium, sulfate, nitrate and chloride ions.
A host of complexes of the type described above and their method of preparation are well known in the leather tanning art. These complexes are described in Shuttleworth and Russel, Journal of the Society of Leather Trades"" Chemists, xe2x80x9cThe Kinetics of Chrome Tannage Part I.,xe2x80x9d United Kingdom, 1965, v. 49, p. 133-154; xe2x80x9cPart III.,xe2x80x9d United Kingdom, 1965, v. 49, p. 251-260; xe2x80x9cPart IV.,xe2x80x9d United Kingdom, 1965, v. 49, p. 261-268; and Von Erdman, Das Leder, xe2x80x9cCondensation of Mononuclear Chromium (III) Salts to Polynuclear Compounds,xe2x80x9d Eduard Roether Verlag, Darmstadt Germany, 1963, v. 14, p. 249; and incorporated herein by reference. Udy, Marvin J., Chromium. Volume 1: Chemistry of Chromium and its Compounds. Reinhold Publishing Corp., N.Y., 1956, pp. 229-233; and Cotton and Wilkinson, Advanced Inorganic Chemistry 3rd Ed., John Wiley and Sons, Inc., N.Y., 1972, pp. 836-839, further describe typical complexes which may be within the scope of the present invention and are incorporated herein by reference. The present invention is not limited to the specific complexes and mixtures thereof described in the references, but may include others satisfying the above-stated definition.
Salts of chromium and an inorganic monovalent anion, e.g., CrCl3, may also be combined with the crosslinking agent complex to accelerate gelation of the polymer solution, as described in U.S. Pat. No. 4,723,605 to Sydansk, which is incorporated herein by reference.
The molar ratio of carboxylate species to chromium III in the chromic carboxylate complexes used in the process of the present invention is typically in the range of 1:1 to 3.9:1. The preferred ratio is range of 2:1 to 3.9:1 and the most preferred ratio is 2.5:1 to 3.5:1.
The additive of the present invention may comprise fibers or comminuted particles of plant materials, and preferably comprises comminuted particles of one or more plant materials.
Fibers suitable for use in the present invention are selected from among hydrophilic and hydrophobic fibers. Incorporation of hydrophobic fibers will require use of a suitable wetting agent. Preferably, the fibers utilized in the present invention comprise hydrophilic fibers, most preferably both hydrophilic and hydrophobic fibers.
With respect to any particular fiber employed in the practice of the present invention, it is believed that the longer the fiber, the more difficult it is to be mixed uniformly in solution. It is believed that fibers as long as 12,500 microns may tend to aggregate and form clumps. The shorter the fiber, it is believed the easier it is to mix in solution. On the other hand, the shorter the fiber, the greater the quantity necessary to provide the desired level of strength in a reinforced mature gel. In general, the fibers utilized in the present invention will have a length in the range of 100 microns to 3200 microns, preferable 100 microns to 1000 microns.